Photographic compositions



United States Patent 3,212,900 PHOTOGRAPHIC COMPOSITIONS Masanobu Oguchi, Yoshimi Kuwabara, Issei Iwai, and

Yasuo Yura, Tokyo, Japan, assignors to Konishiroku Photo Industry Co., Ltd., 'and Sankyo Co. Ltd., Chuoku, Tokyo, Japan, a corporation of Japan No Drawing. Filed Apr. 30, 1963, Ser. No. 276,994

Claims priority, application Japan, May 10, 1962, 37/18,167, 37/18,168 19 Claims. (Cl. 96-109) This invention relates to a stabilized photographic composition, and more particularly, it concerns with a photographic element, e.g., photographic film, paper or plate, bearing on a support a photosensitive layer containing an acetylenically unsaturated compound hereinafter specified.

In the art it is well known that photographic compositions, when stored for a long period after their preparation, suifer f-rom decrease in speed and formation of undesired fog. In order to prevent these adverse efiects, a variety of stabilizers also have been proposed. Incorporation of the known stabilizers, however, is disadvantageous because it usually causes decrease in speed, and the demand in the art has been directed to develop a stabilizer which will permit to prevent fog without any adverse influence on photosensitivity.

It is accordingly one object of the present invention to provide a photographic composition which can resist to any undesired effect caused by storage over a long period of time.

Another object of the present invention is to provide a photographic element which is entirely safe from formation of fog.

Other objects, features, capabilities and advantages which are comprehended by the invention will be apparent from the specification and claims which follow.

The above-mentioned and other objects can be attained by incorporating into a photographic composition a compound, as stabilizer, represented by the general formula wherein R is hydrogen atom or carboxyl, alkoxycarbonyl, phenyl or substituted phenyl radical, and Q is alkoxycarbonyl, carbamoyl,

phenyl, substituted phenyl or naphthyl radical, or in case R represents hydrogen atom, Q may be a group of the formula (in which R represents hydrogen atom, lower alkyl, phenyl, substituted phenyl or aralkyl radical; R represents lower alkyl, phenyl, substituted phenyl, naphthyl or aralkyl radical, or it may, together with the R form a cycloalkyl radical; and R is hydrogen or acyl radical).

We have now found that if the above-specified compound is present in a photographic composition of the present invention, the said composition can be safely stored over a long period of time, without suflering from decrease in speed or formation of fog. In a typical embodiment of the present invention, the specified compound of the general Formula A may be incorporated into at least one of the gelatine comprising layers of a photographic element, such layers including emulsion layers, sub-layers, internal layers, protective layers and backing layers. Another advantage of the present invention is that where the specified compound is added to a 3,212,900 Patented Oct. 19, 1965 photographic emulsion during its ripening or digestion, it is possible to prevent fog formation, and consequently to facilitate an increase of speed due to the ripening or digestion.

Typical compounds of the general Formula A, which can be used efiectively in a photographic composition of the present invention, include the following:

CHaQ-CECH (II) (HQ-CECE (III) BIG-CECE (1V) 02N- -ozon v v @3050]; (VI) onto 0 0-050-0 0 0 0113 VII) mNo o-ozoa (VIII) Q-NHO 0-05011 IX CECC OOH X 0 on, oac-o 0 on (XI) Q-ozo-ooou (XII) cu;o-ozo-o OOH XIII om OH o-czcn (X on -CHaOH-CEC-H XVI CH3 OH CHC-CECH XVII CH3 CH3 CHz-CHz /CECH orn o (XVIII) CH2CHz OH on OHCECH (XIX) on ornQou-czon XX o-ozon (XXI) on-ozorr OH (XXII) co CH3 mQ-on-ozon (XXIII) orn-on-ozon (XXIV) an -omon-ozon (XXV) Some of the above-illustrated compounds are novel substances which have never been prepared and used, and in order to give full and sufficient disclosure in the present specification, our reference will be made hereinunder in connection with the preparative method of such novel substances.

1-t0lyl-2-pr0pyne-1-0l (XX ).A solution containing NaCECH was prepared from 4.6 g. of metallic sodium, about 200 cc. of liquid ammonia, a small quantity of ferric nitrate Fe(NO and gaseous acetylene in the manner heretofore known per se in the art. To the resulted solution, a solution of 24 g. of p-methylbenzaldehyde in 30 cc. of dry ether was added dropwise at 80 C. After completion of the addition, the mixture was stirred at -35 to 40 C. for 5 hours. Then, 15 g. of ammonium chloride was added thereto, and ammonia was vaporized off at room temperature. To the resulted residue, ether and water were added. The ethereal layer separated was removed and then combined with the ethereal extract obtained by shaking the aqueous layer with ether. The combined ethereal portion Was washed with dilute sulfuric acid, aqueous sodium bicarbonate and water, and then dried over sodium sulfate. After evaporation of the ether therefrom, the residual liquid mass was subjected to distillation under reduced pressure to have a fraction (18 g.) boiling at 9698 C./0.8 mm. Hg. This fraction was identified as 1-tolyl-2-propyne-1-ol having the formula OH oua-on-ozon 1-p-chlorophenyl-Z-propyne-I-0l O-acetylate (XXIII). A solution containing NaCECH was prepared from 2.3 g. of metallic sodium, 150 cc. of liquid ammonia, a small quantity of ferric nitrate and acetylene gas in the manner heretofore known per se. To this solution, a solution of 14 g. of p-chlorobenzaldehyde in 20 cc. of dry ether was added dropwise at -80 C. After completion of the addition, the mixture was stirred at 3S to 40 C. for 6 hours. Then, 10 g. of solid ammonium chloride was added thereto and ammonia was vaporized at room temperature. The resulted residue was shaken with ether and water. The ethereal layer was separated, and the aqueous layer was extracted with ether. The ethereal portions were combined, washed with dilute sulfuric acid, sodium bicarbonate and water, and dried over sodium sulfate. After vaporization of ether therefrom, the remaining liquid mass was subjected to distillation thereby to obtain l-(p-chlorophenyl)-2-propyne-1-ol having B.P. 8082 C./0.3 mm. Hg (yield 10 g.). The free alcohol obtained was dissolved in 100 cc. of pyridine and added with 30 cc. of acetic anhydride. The mixture was allowed to stand overnight at room temperature. Then, the mixture was poured into water and extracted with mula OOOCH3 1-phenyl-3-butyne-2-0l (XXV).A G-rignard solution containing HCEC Mg Br was prepared from magnesium (12 g.), ethyl bromide (60 g.), tetrahydrofuran (300 cc.) and gaseous acetylene according to the method described in Organic Synthesis, 39, 56. To the solution prepared, a solution of 55 g. of fresh phenylacetaldehyde in 30- cc. of tetrahydrofuran was added with ice-cooling. After completion of the addition, the resulted mixture was stirred overnight at room temperature. Then it was added with a solution of 50 g. of ammonium chloride in 300 cc. of water with ice-cooling. Ether also was added thereto. The organic solvent layer separated was removed, and the remaining aqueous layer was extracted with ether. The ethereal portions were combined, washed with water until litmus test showed neutral, and then dried over sodium sulfate. After vaporization of the organic solvent, the remaining liquid mass was subjected to distillation in vacuo, thereby yielding 30 g. of 1-phenyl-3-butyne-2-ol (B.P. 65-66 C./0.23 mm. Hg) of the formula Incorporation of the specified compound of the gem eral Formula A into a layer or layers of the photographic element of the present invention can be made in the manner heretofore known per se in the art. For example, where the compound is to be present in an emulsion layer of the said element, it is possible to add the compound into the emulsion at any time just before, during or after the second ripening of the said emulsion. Addition of the compound at the stage after the second ripening of the emulsion is most preferred. Alternatively, the compound may be added to a starting material for preparation of the emulsion, for example gelatine. The amount of the acetylenic compound added will vary depending on the type of emulsions, the class of acetylenic compound used, the degree of stabilization desired and the type of a layer to which the compound is added, but it usually is within the range of 10 mg. to 2 g. per liter of the emulsion or coating solution. It is desirable to add such acetylenic ally unsaturated compound in solution dissolved in a suitable solvent, e.g., water, dilute alkalis, methanol, ethanol, etc., if the addition is made to an emulsion.

Use of the acetylenic ally unsaturated compound as a stabilizer does not adversely influence on sensitization of a photographic emulsion concerned. Thus, the photographic emulsion containing the said unsaturated compound can be sensitized by way of gold-, sulfuror other chemical sensitization or super-sensitization. Furthen more, the acetylenic ally unsaturated compound referred to herein sometimes can provide desirable effect to facilitate an increase of speed because the said compound will prevent increased fog which frequently occurs accompanying to the sensitization. It is of course true that decrease of speed and increase of fog during storage of the emulsion also can be prevented by use of the acetylenic ally unsaturated compound.

Still another advantage of the present invention is tha fog and desensitization both which frequently occur during the storage of a color photographic material containing the large amount of color formers in the emulsion can be efiectively prevented by use of the acetylenic ally unsaturated compound according to the present invention.

The emulsion to which an acetylenic ally unsaturated compound of the general Formula A has been added can be applied to a suitable support in the manner heretofore known per se in the art, e.g., coating or pouring. Suitable supports includes films, papers and glass plates. Particularly suitable are films of the types, such as cellulose esters, e.g., cellulose triacetate; polyesters obtained by the polycondensation of phthalic, isophthalic or terephthalic acid with a dihydric alcohol, e.g., polyethylene terephthalate, poly [cyclohexane-1,4-dimethylol] terephthalate, etc.; and polycarbonates including those obtained by the polycondensation of bis-phenyl A with carbonic acid.

EXAMPLE 1 A silver bromo-iodide emulsion useful for high speed negatives and containing 3% by mole of silver iodide is prepared according to neutral process. This emulsion is subjected to second ripening at a temperature of 60 C. for 75 minutes. After the said ripening, the emulsion is divided to twelve portions, one of which is used for preparation of control film and the other eleven used respectively in combination with the individual member of the acetylenic compounds listed below. Each portions are prepared to form films which in turn are stored at 55 C. for 3 days. Samples of these film coatings were then exposed in an intensity-scale type sensitometor and developed for five minutes in a developer of the following composition:

Grams Metol (p-methylaminophenol sulfate) 2.0 Sodium sulfite (anhydrous) 50.0 Hydroquinon 4.0 Sodium carbonate (monohydrate) 7.0 Potassium bromide 0.75

Water to make 1.0 liter.

The developed samples were stopped with dilute acetic acid and then fixed, Washed and dried. The results are set forth in Table I.

Table I Just after prepara- Incubated at 55 0. Amount of tion of the films for 3 days after compound preparation Compound per liter of emulsion (mg) Relative Fog Relative Fog speed speed Control 100 0. 04 42 0. 75 I 300 100 0. 04 80 0. 15 350 100 0. 04 80 0. 200 100 0.03 85 0.05 600 100 0. 04 95 0. 07 450 100 0. 03 95 0. 06 400 100 0. 04 80 0. 06 200 100 0. 04 60 0. 10 400 100 O. 02 95 0. 05 400 100 0. 04 70 0. 25 420 100 0. 04 70 0.30 420 100 0. 04 85 0. 450 100 0. 04 75 0. 28 400 100 0. 04 85 0. 08

In this test, photographic sensitivity which usually is an inverse number of the amount of light exposure to give an optical density of 0.1 on fog density, is expressed as relative speed to that of unstored control film. The data of Table I clearly indicates that the acetylenic ally unsaturated compounds referred to are useful for prevention of undesired fog.

EXAMPLE 2 The high speed negative emulsion used in Example 1 is subjected to second ripening in the same manner as in Example 1. The treated emulsion is sensitized by addition of dodecyl ethylene oxide lauryl ether in the amount of 100 mg. per liter of the emulsion. The emulsion is divided to portions, each of which is added with the individual member of the acetylenic compounds. Comparative test is conducted in the same manner as in Ex- The data of Table II clearly indicates that the photographic emulsions having been sensitized could be safely stabilized by addition of the acetylenic ally unsaturated compounds.

EXAMPLE 3 To the high speed negative emulsion used in Example 1, sodium thiosulfate is added as sulfur-sensitizer in the amount of 2 mg. per liter of the said emulsion. The resulted emulsion is divided to three portions, on of which is used as control and the other used for the following test. The acetylenic ally unsaturated compound of the Formula IV is added to the second portion at the amount of 300 mg. per liter of the said portion and the acetylenically unsaturated compound of the Formula VIII added to the third portion at the amount of 200 mg. per liter. The resulting mixtures are subjected to second ripening at 60 C., while each samples are collected at the time of 20 min., 40 min., 60 min., min. and min., and coated to film supports. The films obtained are measured in speed and fog according to the procedures described in Example 1. The results are set forth in Table III.

In the above table, relative speed was defined with reference to the value of control having been ripened for 60 minutes as 100. As clearly shown in Table III, speed of the films having been added with the acetylenic ally unsaturated compounds was found to be effectively increased in response to the progress of ripening, with less tendency of fog, while speed of these films was not so appreciably increased in comparison with the control during the initial stage of the second ripening.

EXAMPLE 4 The high speed negative emulsion used in Example 1 is subjected to second ripening at 60 C. for 75 minutes, and then, a solution containing l- (4-phenoxy-3-sulfophenyl) 3-heptadecyl-5-pyrazolone as a color former is added thereto. The resulted emulsion is coated onto a film base. Onto the surface of the resulted film, 3% gelatine solution incorporated with or without the listed compound is applied as protective layer to have a multilayer film. The resultant film is stored at 55 C. for 3 days in the same manner as in Example l, The abovettreated film, as well .as untneated film, are developed with a color developing solution containing diethylap-phenylone diam-inc. The developed films ewe bleached, fixed and water-washed in the customarily known manner. The results obtained are set forth in Table IV.

Table IV Amount Just after prepara- Iucubated at 55 0. added to 1 1. tion of the films for 3 days after Compound of 3% gelapreparation used tine solution Relative Fog Relative Fog speed speed The data of .'I:ab=le IV clearly indicates that fog formation can be prevented by the presence of the acetylenic com pounds in protective layer.

EXAMPLE pounds listed below. Each portion is prepared to [form films which in turn are stored at 55 C. tor three days. Speed and fog of the films are determined in the same manner as in Example 1. The results are set forth in Table V.

Table V Just after prepara- Incubated at 55 C. Amount of tion of the films for 3 days after compound preparation Compound per liter of emulsion (mg) Relative Fog Relative Fog speed speed The data of Table V clearly indicates that iog formation is prevented by addition of the :aoetylenic ally unsaturated compounds of the invention.

Modifications of the present invention will be apparent for those skilled in the art. It is, therefore, to be understood that in lieu of the (acetylenic compounds of the loregoing examples, we may use any one or more of the lacetylenic compounds defined by the aforementioned general Formula A and that the acetylenic compounds referred to herein may be used singly or in combination with the customarily known stabilizers and antifoggant, without any undesired effects.

What We claim is:

1. A light-sensitive, photographic silver halide composition comprising light-sensitive silver halide and, as the stabilizer therefor, an acetylenically unsaturated compound represented by the general formula in which R is one member selected from the group consisting of hydrogen atom, carboxyl, allooxycarb-onyl, phenyl and substituted phenyl radicals, and Q is one memher selected from the group consisting of alkoxycarbonyl,

carbamoyl,

phenyl, substituted phenyl and naphthyl radicals, and in case R represents hydrogen atom, Q may represent a group of the formula R1 OR;

R2 wherein R represents one member selected from the group consisting of hydrogen atom, lower alkyl, phenyl, substituted phenyl and saralkyl radicals; R represents one member selected from the group consisting of lower alkyl, phenyl, substituted phenyl, naphthyl and aralkyl radicals, and both R and R may tori-n together cycl-oalkyl radical; and R is one member selected from the group consisting of hydrogen atom and acyl radical.

2. A light-sensitive, photographic silver halide composition comprising light-sensitive silver halide and phenyl acetylene as the stabilizer therefor.

3. A light-sensitive, photographic silver halide composition com-prising light-sensitive silver halide and pbromophenyl acetylene as the stabilizer therefor.

4. A light-sensitive, photographic silver halide composition comprising light-sensitive silver halide and carbamoyl acetylene as the stabilizer thereior.

5. A light-sensitive, photographic silver halide composition comprising light-sensitive silver halide and diacetyl acetylene as the stabilizer therefor.

6. A light-sensitive, photographic silver halide composition comprising light-sensitive silver halide and phenyl propiolic acid as the stabilizer therefor.

-7. A light-sensitive, photographic silver halide composition comprising light-sensitive silver halide and fi-ethynyl naphthalene as the stabilizer therefor.

8. A light-sensitive, photographic silver halide compo sition comprising lightasensitive silver halide and p chlo-ropheny-l acetylene as the stabilizer therettor.

9. A light-sensitive, photo-graphic silver halide compo sition comprising light-sensitive silver halide and l-phenyl- 2-propyne-1-ol as the stabilizer therefor.

10. A light-sensitive, photographic silver halide emulsion comprising gelatin having light-sensitive silver halide dispersed therein and containing as a stabilizer an acetylenically unsaturated compound represented by the general iormula in Which R is one member selected from the group consisting of hydrogen atom, carboxyl, lallooxycarbonyl, phenyl and substituted phenyl radicals, and Q is one rnem ber selected from the group consisting of alkoxycarbonyl,

carbarn-oyl,

phenyl, substituted phenyl and naphthyl radicals, and in case -R represents hydrogen atom, Q may represent a group of the formula .11. A light-sensitive, photographic silver halide emulsion as claimed in claim '10; further comprising a member selected from the group consisting of sulfur, gold- :and reductive sen'sitizers.

'12. A light-sensitive, photographic silver halide emulsion as claimed in claim '10; further comprising a surface active agent.

13. A light-sensitive, photographic silver halide emulsion as claimed in claim 10; further comprising :an optical sensitizerr.

14. A light-sensitive, photographic silver halide emulsion as claimed in claim .10; further comprising a color dormer.

15. A photographic element comprising a support hearing thereon a layer of the light-sensitive photographic silver halide emulsion as claimed in claim .10.

1 6. A photographic element as claimed in claim 15; wherein said support is a film mainly consisting of a polymeric material selected firom the group consisting lOf cellul osic esters, polyesters and p olycarbonates.

.1 7. A photographic element as claimed in claim 16; wherein said film is cellulose triacetate film.

1 8. A photographic element (as claimed in claim 16; wherein said film is polyethylene terephthalate film.

19. A photographic element as claimed inclaim 16; wherein said film is a film of the poly condensation prodnot of bis-phen ol A and carbonic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,150,702 3/ 39 Sheppard et al 96109 2,897,081 7/59 Dersch et a1. 96109 3,040,047 6/62 Siraloawa 96-409 3,043,697 7/62 Forsgard 9 6109 NORMAN G. TORCHIN, Primary Examiner. 

1. A LIGHT-SENSITIVE, PHOTOGRAPHIC SILVER HALIDE COMPOSITION COMPRISING LIGHT-SENSITIVE SILVER HALIDE AND, AS THE STABILIZER THEREFOR, AN ACETYLENICALLY UNSATURATED COMPOUND REPRESENTED BY THE GENERAL FORMULA 